Light sensitive color photographic material

ABSTRACT

A LIGHT-SENSITIVE SILVER HALIDE COLOR PHOTOGRAPHIC MATERIAL CONTAINING A COMPOUND OF THE GENERAL FORMULA, 1-(X,Y,Z-PHENYL),3-((2-(R3-O-)PHENYL)-O-CH(-R1)-CO(A)(M-1)-NH-),4-W,5-(O=)-2-PYRAZOLINE WHERE W IS A HYDROGEN ATOM, OR A PHENYLAZO GROUP; X, Y AND Z, WHICH MAY BE SAME OR DIFFERENT, ARE INDIVIDUALLY A HYDROGEN OR HALOGEN ATOM, A LOWER ALKYL GROUP, A LOWER ALKOXY GROUP, A PHENYL GROUP OR A GROUP OF THE FORMULA COOR3(WHERE R3 IS A LOWER ALKYL GROUP); A IS A DIVALENT GROUP OF THE FORMULA -NH-(PHENYLENE(-R4))-, -NH-PHENYLENE-CO- OR -NH-PHENYLENE-NH-CO(WHERE R4 IS A HYDROGEN OR HALOGEN ATOM); M IS AN INTEGER OF 1 OR 2; R1 IS A HYDROGEN ATOM OR A LOWER ALKYL GROUP; AND R2 IS AN ALIPHATIC HYDROCARBON RESIDUE HAVING 8 TO 16 CARBON ATOMS.

States Patent 3,761,274 LIGHT-SENSITIVE COLOR PHOTOGRAPHIC MATERIALIsaburo Inoue, Teruo Hanzawa, and Takaya Endo, Tokyo, Japan, assignorsto Konishiroku Photo Industry Co., Ltd., Tokyo, Japan No Drawing. Filed'July 9, 1971, Ser. No. 161,953

Claims priority, application Japan, July 10, 1970, 45 3 3 Int. Cl; G03c1/40 5 Claims U.S. c1. 96-5100,

ABSTRACT on THE DISCLOSURE A light-sensitive silver halidecolorphotographic material containing a compound of the general formula,

0: /N 1 (BR:

where W is a hydrogen atom, or a phenylazo group; X, Y and Z, which maybe same or diflerent, are individually a hydrogen or halogen atom, alower alkyl group, a lower alkoxy group, a phenoxy group or a group ofthe formula COOR, (where R is a lower alkyl group); A is a divalentgroup of the formula NH-e NH or s V (where R, is a hydrogen or halogenatom); ml is an integer of 1 or 2; R is a hydrogen atom or a lower alkylgroup; and R is an aliphatic hydrocarbon residue having 8 to 16 carbonatoms.

wherein X, Y and Z, which may be same or difierent, are individually:ahydrogen or a halogen :"atom'; a lower alkyl group, a lower alkoXy"group; a phenoxy" group or a 3,761,274 Patented Sept. 25, 1973 group ofthe formula COOR (where R is a lower alkyl group); A is a divalent groupof the formula NH- (where R, is a hydrogen or halogen atom); in is aninteger of 1 or 2; R is a hydrogen atom or a lower alkyl group; W is ahydrogen atom or a phenylazo group; and R is an aliphatic hydrocarbonresidue having 8 to 16 carbon atoms.

Heretofore, many compounds have been proposed as protect type couplers.These couplers,'however, have various drawbacks, and there have scarcelybeen known those which can be prepared at lower cost with higher purity.

For example, the coupler disclosed in US. Pat. No. 2,

428,054 which has the general formula,

H2C HJ NHCOC1EHS1 the coupler disclosed in US. Pat. No. 2,694,703 whichhas the general formula,

and the coupler disclosed in Japanese patent publication No. 28,114/1964 which has the general formula,

can be synthesized easily and at relatively low cost. These couplers,however, have low solubility in high boiling solvents and are readilycrystallizable, so that it is extremely difficult to use them ascouplers of the protect type.

In contrast thereto, the coupler of the aforesaid general formula whichis used in the present invention can be prepared simply and economicallyby utilizing a certain color-forming nucleus and by using as startingmaterials alkyl bromide and catechol which can be obtained com-.merically with ease and at low cost. The thus prepared coupler iseasily soluble in a high boiling solvent such as phthalate or tricresylphosphate, so that the amount of solvent for the coupler can bedecreasedto make it possible to obtain a highly concentrated dispersion.Moreover, the coupler synthesized in the above'manner has a low meltingpoint and hence has the characteristic that it is diflicultlycrystallized in a photographic emulsion or in a film formed by coatingand drying the emulsion. Further, the light-sensitive color photographicmaterial according to the present invention which has been incorporatedwith said coupler is favorable in durability and easily soluble in ahigh boiling solvent, so that the photographic material is excellent inspectral absorption characteristic and can give a color image which isfavorable in transparency and high in density.

'The coupler used in the present invention may be synthesized accordingto, for example, the following procedures:

A long chain alkyl bromide and catechol are condensed with indimethylformamide in the presence of potassium bicarbonate to form acatechol monoalkyl ether, which is then condensed with a halogeno-fattyacid to obtain a long chain alkoxyphenoxy fatty acid. Subsequently, thisacid is treated with phosphorus pentachloride to form the correspondingacid chloride, which is then condensed with a coupler component havingan amino group, whereby the coupler used in the present invention can besynthesized.

Typical examples of the coupler having the aforesaid general formula areset forth below, but couplers usable in the present invention are notlimited to these examples.

HiC-ICNHC 0 CH-O- 0: N 2H5 1-phenyl-3- [a- (2-dodecyloxyphenoxy)buty1amtde1- -pyrazolone HzO-fi-NHC 0 CH-O O= 2 5 1- (-methoxyphenyl)-3- [a- (Z-tetradecyloxyphenoxy) buty1amlde1-5-pyrazolone (3) O CaHu 1-[4- (4-t-butylphenoxy) phenyl] -3- [a- (octyloxyphenoxy)proplonamide]-5-pyraz01one 1- 4-ethoxycarbonylphenyl) -3- a-(2-hexadecyloxypheuoxy) butylamide1-5-pyrazolone 1- (2,4-dlmethyl-6chlorophenyl) -3- [a- (2-dodecyloxyphenoxy) butylamide1-5-pyrazolone 1-(2,6-dichloro-4-methoxypheny1) -3 [a- (2-dodecyloxyphenoxy)buty1am1de1-5-pyrazo1one (8) NHCQCH-O 1-phenyl-3-{3- [a-(2-dodecyloxyphenoxy) butylamide] benzamtde}-5-pyrazo1one NHGOCHIO 0 0Has 1- (2,4,6-tr1ch1orophenyl) -3- [3- (2-dodecyloxyphenoxy) acetamide]benzamlde-fi-pyrazolone niiooonzo- 1- (2,4,6 trichloroplienyl) -3- [3(2-dodecyloxyphenoxyacetj amide)benzoureideyfi pyrazolone I OH: 1

1- (2,6-dichloro'4-methoxyphenyl) -8-{4- [a- (2-dodecy10xyphenoxy)butylamide] benzoureide}-5-pyrazolone l 1- (2,4,6-triclhlorophenyl)-3-{4-[a- (2-dodecy10xyphenoxy) 1 nncocmo V 2,4,6-trlchloropheny1) -3-[3-(2-dodecyloxyphenoxy) acetamide] benzamide-4- (Qmethoxy-phenylazo)-5-pyrazo1one Concrete synthesis examples of typical couplers amongthose having the aforesaid general formula are set forth below.

(a) A mixture comprising 110 g. of catechol, 500 ml. ofdimethylformamide, 140 g. of potassium carbonate and 280 g. of dodecylbromide was stirred at 110 to 120 C. for 3 hours and then poured intowater. The oily layer formed was extracted with ether, and the extractwas washed with water and then dried with anhydrous sodium sulfate.Subsequently, the ether was removed by distillation, and the residue wassubjected to distillation to obtain a fraction of catechol monododecylether, B.P. 203205 C./ 2 mm. Hg. yield In the same manner as above,there were obtained catechol monooctyl ether, B.P. 180-3 C./4 mm. Hg;decyl ether, B.P. 192-3 C./4 mm. Hg; tetradecyl ether, B.P. 220-5 C./4mm. Hg; and hexadecyl ether, B.P. 225-8 C./ 3 mm. Hg.

(b) A solution of 13.8 g. of metallic sodium in 300 ml. of alcohol wasmixed with 86.5 g. (0.3 mole) of catechol monododecyl ether, and theresulting mixture was boiled for 30 minutes. Thereafter, the mixture wascharged with 50.5 g. (0.3 mole) of a-bromobutyric acid, boiled for 3hours, poured into ice water with stirring and then acidified withhydrochloric acid to form a precipitate. This precipitate was recoveredby filtration, dried and then recrystallized from hexane to obtainu-(2-dodecyloxyphenoxy) butyric acid, M.P. 746 C., yield 75%.

In the same manner as above, there were obtained long chainalkoxyphenoxy fatty acids to be used in the synthesis examples shownlater. For example, 2-dodecyloxyphenoxy acetic acid, M.P. 6870 C., wassynthesized from catechol monododecyl ether and monochloroacetic 647 C.,from resorcinol monooctyl ether and a-bromopropionic acid; andu-(Z-hexadecyloxyphenoxy)butyric acid, M.P. 8 C., from resorcinolmonohexadecyl ether and a-bromobutyric acid.

(0) The thus obtained long chain alkoxyphenoxy fatty acid is formed intoan acid chloride by treament with phosphorus pentachloride. For example,a suspension of 36.4 g. of 2-dodecyloxyphenoxy acetic acid in ml. ofchloroform is charged with 23 g. of phosphorus pentachloride, allowed tostand for 30 minutes and then heated for 30 minutes in a water bath keptat 60 C. Thereafter, by-produced phosphorus oxychloride and chloroformare removed by distillation under reduced pressure, and the residualchloride is used in the subsequent acylation step.

SYNTHESIS EXAMPLE 1 A mixture comprising 7.02 g. of 1-phenyl-3-amino-5-pyrazolone, 21 ml. of acetonitrile, 4 ml. of pyridine and 14.60 g. ofthe chloride described in the abovementioned item (0) was refluxed for 1hour and then poured into a liquidmixture consisting of 210 ml. of waterand 21 ml. of concentrated hydrochloric acid to deposit a brown oilysubstance.

After removing the mother liquor by decantation, the oily substance wasdissolved in ethyl acetate and dried with anhydrous sodium sulfate, andthen the solvent was removed by distillation under reduced pressure. Theresidual brown oily substance was dissolved in 200 ml. of hexane todeposit a white precipitate, which was then recovered by filtration,washed with a small amount of hexane and then dried to obtain 12.0 g.(57.4%) of a White powder, M.P. 667 C.

The thus obtained product was the exemplified Compound 1.

In the same manner as above, the exemplified Compounds 2 to 14 could besynthesized by the condensation of acid chloride having a differentalkayl chain with nuclei having different substituents.

The melting points and nitrogen analysis values of the TABLE1.COMPARISON OF MELTING POINT AND SOLUBILITY BETWEEN COUPLERS USEDPRESENT INVENTION AND KNOWN COUPLERS SIMILAR IN STRUCTURE THERETO 8SYNTHE/S/IS EXAMPLE 2 1.8 grams of p-anisidine was 'diazotized with asolution comprising-20.0 mlf of water, 5.0 ml. of concentratedhydrochloric acid and 1.2 g. of sodium nitrite, and 40 ml. of alcoholwas added to the resulting di-a'zonium salt. This diazonium saltsolution was added at 5 to 10 C. to a solution of 7.2 g. of theexemplified (coupler (9) in 72 ml. of pyridine. The mixed solution wasstirred for 3 hours and then diluted ,with 300 of water, and 80 ml. ofconcentrated hydrochloric acid was added to the resulting dilution todeposit a precipitate. Subsequently, the precipitate was recovered byfiltration, washed with water, dried and then recrystallized fromligroin to obtain an orange powder, M.P. 58-60 C. The thus obtainedproduct was the exemplified coupler (l5).

Nitrogen analysis: Calculated: 9.88%. Found: 9.70%.

Tests were carried out in order to substantiate the fact that thecouplers used in the present invention have a low melting point andexcellent solubilityin high boiling solvents. The results obtained wereas set forth in Table -1, in which are also shown for comparison theresults obtained in the case of known couplers.

I THE C. Solubility Coupler Structure Exemplitied coupler (7)....- 0 CHE66-7 3.0

CHr--CNHC O CH-O O=l\ /N 3 5 Coupler disclosed in U.S; 2

Pat. 2,694,703. CHz-fi-NHC O CHQO tCsHu o: t0 H 1 N a i Exemplifiedcoupler (9) I -7 2. 0 CHz-(" NHC O 0 01:11:: O= N N HO 0 CHaO C1 Couplerdisclosed in U.S. 138-139 11. 0

at. CHr-fi-NHCO Y o= i N r v \N/ NBC 0 CHaO tCgHu t 01111 C1 C1 1Substantially insoluble:

In Table l, the solubility in high boiling solvent is represented by theamount (ml.) of dibutyl phthalate necessary to dissolve 1 g. of eachcoupler.

As is clear from Table 1, it is understood that the couplers used in thepresent invention have a low melting point and excellent solubility inhigh boiling solvents as compared with the known couplers, and hence arequite useful as protect type couplers.

. In the next place, test results showing the fact that the low boilingsolvent by water-washing or the like treatment and incorporated into asilver halide photographic emulsion, which is then coated on such asupport as mentioned above and dried to prepare a light-sensitive colorphotographic material.

The above-mentioned incorporation procedure is illustrative and is notlimitative. In the above case, the amount of the coupler to beincorporated into the photographic emulsion is ordinarily to 100 g. permole of the silver couplers according to the present invention givecolor 10 halide contain! therein, but is P ye lifflited to imagesexcellent in spectral absorption characteristics Sald range and 1SVarlable aceofdlng t0 applleatlon P are set forth in Table 2. P

In Table 2, Al is the diiferencebetween the absorp- Further, the couple?may be mcorporatf'd mm flon Wave length M m at [D]=0 2 and Am (m) atmore different emulsion layers of a mult1-layered light- 1 0 i Vthe longwave id adsorption Zone, and sensitive color photographic material. Theemulsion used M is the diiference between the absorption wave length inthe Present invefltlon y contain y of Various Silver t [D]=0 4 land x tth h t wave id b halides such as silver chloride, silver iodobromide and11 Zone, silver chlorobromide, and may have been incorporated A) =D witha chemical sensitizer, e.g. sulfur sensitizer, a na- =0\ -7\ turalsensitizer present in gelatin, a reducing sensitizer or TABLE 2 am. AMA),

Known coupler N/ NHOOCH O 45051111 tCtHn C1 C1 Known coupler Exemplifiedcoupler:

The results set forth in Table 2 are measured values of a noble metalsalt. The emulsion may further contain, color images'formed according toExample 1. ordinary photographic additives such as, for example,

Fr m he re l s of T le i is understood h the antifoggant, stabilizer,anti-stain agent, anti-irradiation couplers used in the present nventiongive color Images agent, physical property-improving high polymerddiexcelleht specfral Ql characterfstlctive, film hardener, coating aid,etc. Furthermore, the F P fh couPlers used f P emulsion may contain aknown carbocyanine dye, merolnventloninto llght-sensltlve colorphotographic materials, cyanine dye or the like as an optical sensitizerfor the there may be adopted any of the known procedures. For emulsion.gt i e.9 i f yg f q i q i The thus obtained light-sensitive colorphotographic i ma m a 1g so avmg a 011 g material is exposed to radioactive rays such as a-rays, ppomt of more than 175 C., such as trlcresylphosphate f d h rk d 1 d or dibutyl phthalate, a low boiling solventsuch as butyl y V151 e rays {are rays or t e 1 I ope acetate or butylpropionate, or a mixture of said two with a .developer contammg ali-phenylenedlamlpe type solvents. Subsequently,'the resulting solutionis mixed dFVekPPmg and then sublected bleiichmg with an aqueousgelatin-solution containing a surfactant sllvemfg and fixmg trezfltmentsto obtam 3' hlgh denvslty and than emulsified by means of a high speedrotary color image excellent in spectral absorption charactermixer or acolloid mill. Thereafter, the resulting emul- 13m and duliablllty andfavorable pe ysion is directly incorporated into a 1ight-sensitivesilver Furthermore, a $0101 p e p ie contamhalide photographic emulsionand coated on a support 2 the e p 0f the P e e lIlventlel'l can glve a90101 such as a glass plate, synthetic resin plate, film base or imageof Improved durablhty when the photogra hic m alaminated paper, and thena major proportion of the low terial is incorporated with an ultravioletabsorber of the boiling solvent is removed by drying to prepare alight-senbenzophenone type, e.g. 2-hydroxy-4-dodecyloxybenzo sitivecolor photographic material. Alternatively, the said phenone, or of thetriazole type, e.g. 2-(2'-hydroxy-3',5'- coupler emulsion is once set,finely cut, freed from the di-tert-butylphenyl)benzotriazole. v

Typical examples of the deveolping agent used for de velopment of thelight-sensitive color photographic material of the present invention aresulfates, sulfites and hydrochlorides of the following:

N,N-diethyl-p-phenylenediamine,

N-ethyl-N-B-methanesulfonamidoethyl-3methyl-4- aminoaniline,

N-ethyl-N-hydroxyethyl-p-phenylenediamine,

N-ethyl-N-hydroxyethyl-Z-methyl-p-phenylenediamine andN,N-diethyl-Z-methyl-p-phenylenediamine.

Further, the color developer used for development of the photographicmaterial may contain, in addition to the above-mentioned developingagent, a developmentcontrolling agent such as citrazinic acid or thelike.

The present invention is illustrated in further detail below withreference to examples, but the examples are illustrative and it isneedless to say that the invention is not limited only to theseexamples.

EXAMPLE 1 10.0 grams of the exemplified coupler (9) was added to a mixedsolvent comprising 10 ml. of dibutyl phthalate and 30 ml. of butylacetate and then heated to 60 C., whereby the coupler was completelydissolved to form a solution. This solution was mixed with ml. of aaqueous solution of Alkanol B (alkylnaphthalene sulfonate produced andsold by Du Pont) and with 100 ml. of a 5% aqueous gelatin solution, andthe mixed solution was subjected to a colloid mill to prepare adispersion.

This coupler dispersion was incorporated into 1 kg. of a high speedlight-sensitive gelatinous silver iodobromide photographic emulsion,which was then coated on a film base and dried to obtain alight-sensitive photographic film.

The thus obtained photographic film was exposed according to an ordinaryprocedure and then developed at 20 C. for 10 minutes with a developer ofthe following composition:

3-sodium N-ethyl-N-B-methane-sulfonamidoethyl-3-methyl-4-aminoanilate.12H O 5.0 Anhydrous sodium sulfite 2.0 Benzylalcohol 3.8

Sodium carbonate (monohydrate) 50.0 Potassium bromide 1.0 Caustic soda0.55 Water to make 1,000 ml.

Subsequently, the developed photographic film was subjected to ordinarystopping and fixing treatments, washed with water for 10 to minutes andthen treated for 5 minutes with a bleaching solution of the followingcomposition:

G. Potassium ferricyanide 100 Potassium bromide 50 Water to make 1,000ml.

Thereafter, the thus treated photographic film was washed with water for5 minutes, fixed for 5 minutes in a fixing bath comprising 250 g. ofsodium thiosulfate and 1,000 ml. of water, washed with water for to mmutes and then dried to obtain a clear magenta color image having anabsorption maximum at 550 mu.

EXAMPLE 2 subjected to a colloid mill to prepare a coupler dispermen.

This dispersion was incorporated into 500 g. of a gelatin silveriodobromide emulsion, which was then coated on a film base and dried toobtain a photographic film.

The thus obtained photographic film was exposed and then developed at 21C. for 12 minutes with a developer of the following composition:

G. Metol 3.0 Anhydrous sodium sulfite 50.0 Hydroquinone 6.0 Anhydroussodium carbonate 40.0 Potassium bromide 3.5 Potassium rhodanate 2.0

Water to make 1,000 ml.

Subsequently, the developed photographic film was subjected to ordinarystopping, hardening and water-washing treatments, and then to secondaryexposure by use of a white light. Thereafter, the photographic film wasdeveloped at 21 C. for 13 minutes with a developer of the followingcomposition:

G. N,N-diethyl-2-methyl-p-phenylenediamine 3.0 Anhydrous sodium sulfite4.0 Sodium carbonate (monohydrate) 20.0 Potassium bromide 2.0

Water to make 1,000 ml.

The thus developed photographic film was subjected to ordinary stopping,water-washing, bleaching and fixing treatments, washed with runningwater for 20 minutes and then dried to obtain a positive magenta colorimage having an absorption maximum at 540 me which was excellent intransparency.

EXAMPLE 3 10 grams of the exemplified coupler (l) was mixed with 20 ml.of dibutyl phthalate and then heated to 50 C., whereby the coupler wascompletely dissolved to form a solution. This solution was mixed with 5ml. of a 10% aqueous solution of Alkanol B and with 200 ml. of a 5%aqueous gelatin solution, and the mixed solution was subjected severaltimes to a colloid mill to prepare a coupler dispersion. This dispersionwas incorporated into 500 g. of a gelatin silver chlorobromide emulsion,which was then coated on a baryta paper and dried to produce alightsensitive photographic material.

The thus produced photographic material was exposed and then developedat 25 C. for 10 minutes in a bath of the following composition:

N ethyl-N-fl-methane-sulfonamidoethyl-3-methyl-4- aminoaniline sulfate g3-sodium sulfate.12H O g 15.0 Sodium metaborate g Water to make 1,000ml:

The developed photographic material was dipped for 2 to 4 minutes in astopping and fixing bath of the following composition:

Ammonium thiosulfate g Potassium metabisulfite g 20 Glacial acetic acidcc..- 10

Water to make 1,000 ml.

13 The thus treated photographic material was washed with water forminutes and then bleached at 25 C. for 3 minutes in a bath of thefollowing composition:

G. Sodium nitrate 28.0 Potassium ferricyanide 10.0 Boric acid 7.5Potassium bromide 7.5

Water to make 1,000 ml.

EXAMPLE 4 2.0 grams of the exemplified coupler (15) was added to a mixedsolvent comprising 2 ml. of dibutyl phthalate and 6 ml. of butylacetate, and then heated to 60 C., whereby the coupler was completelydissolved to form a solution. This solution was mixed with 1 ml. of a10% aqueous solution of Alkanol B and with 20 ml. of a 5% aqueousgelatin solution, and then emulsified to prepare a coupler dispersion.Subsequently, the coupler dispersion was incorporated into 100 g. of ahigh speed silver iodobnomide photographic emulsion, which was thencoated on a film base and dried to produce a lightsensitive photographicfilm.

This photographic film was exposed according to an ordinary procedureand then treated according to the same color development procedures asin Example 1 to obtain a yellow positive image having an absorptionmaximum at 440 mg and a magenta color image having an absorption maximumat 550 me.

What we claim is:

1. A light-sensitive silver halide color photographic materialcharacterized by containing a compound of the general formula,

wherein W is a hydrogen atom, or a phenylazo group; X, Y and Z, whichmay be same or different, are individually a hydrogen or halogen atom, alower alkyl group, a lower :alkoxy group, a phenoxy group or a group ofthe formula COO R (where R is a lower alkyl group); A is a divalentgroup of the formula NH- NH- (where R is a hydrogen or halogen atom); mis an integer of 1 or 2; R is a hydrogen atom or a lower alkyl group;and R is an aliphatic hydrocarbon residue having 8 to 16 carbon atoms.

2. The light-sensitive silver halide color photographic material ofclaim 1 wherein said compound is 1-(2,4,6- tn'chlorophenyl) 3(2-dodecyloxyphenoxyacetamide)-5- pyrazoline.

3. The light-sensitive silver halide color photographic material ofclaim 1 wherein said compound is 1-(2,4- dimethyl 6chlorophenyl)-3-[a-(2-dodecyloxyphenoxy) butylamide}5-pyrazolone.

4. The light-sensitive silver halide color photographic material ofclaim 1 wherein said compound is 1-(2,4,6- trichlorophenyl) 3[3-(Z-dodecyloxyphenoxy)acetamide] benzamide-S-pyrazolone.

5. The light-sensitive silver halide color photographic material ofclaim 1 wherein said compound is 1-(2,4- dimethyl6-chlorophenyl)-3-{3-[a-(Z-dodecyloxyphenoxy)butylamide]benzamide}-5-pyrazolone.

References Cited UNITED STATES PATENTS 2,369,489 9/1942 Porter et a1.96100 2,908,573 10/1959 Bush et al. 96-565 3,700,454 10/ 1972 Sakamotoet #al 96100 NORMAN G. TORCHIN, Examiner R. L. SCHILLING, AssistantExaminer

